Electrophoretic assembly of electrochemical devices

ABSTRACT

Methods are provided for making bipolar electrochemical devices, such as batteries, using electrophoresis. A bipolar device is assembled by applying a field that creates a physical separation between two active electrode materials, without requiring insertion of a discrete separator film or electrolyte layer.

This application is a continuation of U.S. patent application Ser. No.11/108,602, filed Apr. 18, 2005, which claims priority to U.S.Provisional Patent Application Ser. No. 60/563,026, filed Apr. 16, 2004,and U.S. Provisional Patent Application Ser. No. 60/583,850, filed Jun.29, 2004. U.S. patent application Ser. No. 11/108,602 is also aContinuation In Part of U.S. patent application Ser. No. 10/206,662,filed Jul. 26, 2002, which claims priority to U.S. ProvisionalApplication Ser. No. 60/308,360, filed Jul. 27, 2001; U.S. patentapplication Ser. No. 10/206,662 is also a Continuation In Part of U.S.patent application Ser. No. 10/021,740, filed Oct. 22, 2001, whichclaims priority to U.S. Provisional Patent Application Ser. No.60/242,124, filed Oct. 20, 2000. Each of these applications areincorporated by reference herein.

GOVERNMENT RIGHTS

This invention was made with government support under Grant NumberF49620-02-1-0406, awarded by the Air Force, and Grant NumberNMA501-03-01-2004, awarded by the Department of Defense. The governmenthas certain rights in the invention.

BACKGROUND

1. Field

The field includes methods of making bipolar devices using electricalpotentials and electric fields, and in particular methods of makingbipolar electrochemical devices, such as batteries, usingelectrophoresis.

2. Summary of the Related Art

Batteries, and particularly rechargeable batteries, are widely used in avariety of devices such as cellular telephones, laptop computers,personal digital assistants, and toys. Manufacturing constraintsgenerally limit the available shapes of batteries, with common formfactors including cylinders, button cells (thin discs), and prismaticforms. The energy density of such batteries is relatively low, due topoor volumetric utilization of space within the electrochemical devices.Recently “three-dimensional batteries” have been proposed, which haveanodes and cathodes with active surface areas exposed in threedimensions, and potentially exhibit improved performance resultscompared to standard battery geometries. A need exists for newmanufacturing methods to create electrochemical devices with improvedenergy density, power density, and cycle life, as well as reducedmanufacturing cost.

Electrophoresis, the motion of charged particles under an appliedelectric field, is used to characterize the behavior of solutions andsuspensions, and has also been used to deposit materials in the form ofthin films, coatings, and even bulk products. The formation of batteryelectrodes by electrophoretic deposition has been disclosed (e.g.,Kanamura et al., Electrochemical and Solid-State Letters, 3:259-262(2000)). Typically, a coating is electrophoretically deposited on ametal substrate from a suspension of particles in a liquid. Thedeposited coating is then removed from the apparatus or bath in whichthe deposition was carried out, and subsequently used for a desiredapplication. For example, to prepare a battery, anelectrophoretically-deposited electrode is removed from its liquiddeposition bath, dried, and used as a component in a device assembly.However, the act of electrophoresis does not by itself create a completedevice.

SUMMARY

Methods are provided for making bipolar electrochemical devices usingelectrophoresis. Potentials (e.g., electrical potentials) and fields(e.g., electrical fields) are used to assemble a variety ofelectrochemical device architectures, including two-dimensional andthree-dimensional constructions for batteries, capacitors, fuel cells,electrochromic displays, and sensors. The disclosed electrophoreticassembly methods do not require insertion of a discrete separator filmor electrolyte layer, and are useful for producing devices with reducedmanufacturing cost and improved energy density, power density, and cyclelife.

In certain embodiments, the methods described herein utilize theelectric-field assisted deposition of an electroactive material from amedium. The electroactive material is suspended in the medium, and maybe in the form of colloidal particles, macromolecules, molecules, orions. Hereafter, it should be understood that the term “particles”refers to any of the above forms.

One aspect provides a method of assembling a bipolar device including afirst terminal and a second terminal, and a device made according to themethod. The method includes providing the first terminal and providingparticles of a first electroactive material in a medium. The methodfurther includes providing the second terminal electronically connectedto a second electroactive material. The method further includesgenerating a field causing particles of the first electroactive materialto form an electronically continuous electrode, and creating anelectronically insulating separation between the first and secondelectroactive materials. The electronically insulating separationbetween the first and second electroactive materials is preserved in thefinal device.

In certain embodiments, the method comprising generating an electricalfield causing particles of the first electroactive material to form anelectronically continuous electrode, and creating an electronicallyinsulating separation between the first and second electroactivematerials. The electrical field can be generated by applying anelectrical potential between the first terminal and the second terminal;or, between one of the first and second terminals and a third terminal.The electrical field can attract particles of the first electroactivematerial to the first terminal. In some cases, the electrical fieldattracts particles of the first electroactive material to the firstterminal and/or repels particles of the first electroactive materialfrom the second electroactive material in the medium.

In certain embodiments, the method also includes providing an ionicallyconductive material in the electronically insulating separation betweenthe first and second electroactive materials. In some embodiments, theionically conductive material is a liquid electrolyte. In someembodiments, the medium includes a polymer, and preserving theelectronically insulating separation between the first and secondelectroactive materials includes solidifying, or drying, the polymer toform a solid polymer electrolyte.

In some embodiments, the method further comprises depositing particlesof the first electroactive material on the first terminal.

In certain embodiments, the second electroactive material has athree-dimensional structure defining a void space, and wherein the fieldcauses particles of the first electroactive material to concentrate inthe void space. The second electroactive material may be a porouselectrode, and wherein the field causes particles of the firstelectroactive material to concentrate in the pore space of the porouselectrode. The porous electrode may be a reticulated open-cell carbon,metal or ceramic foam.

In some embodiments, wherein particles of at least one of the first andsecond electroactive materials are coated with a conductive material.

In some embodiments, at least one of the terminals is patterned toinclude a serpentine, spiral, or comb-like region and further comprisingdepositing electroactive material in the region. In some cases, thefirst and second terminals are constructed and arranged to beinterdigitated.

In some embodiments, the method further comprises depositing particlesof the first electroactive material on the first terminal therebyforming an electronically continuous first electrode; and, generating asecond field causing particles of the second electroactive material todeposit on the second terminal, thereby forming an electronicallycontinuous second electrode. The method may further comprise creating anelectronically insulating separation between the first and secondelectrodes; and, preserving the electronically insulating separationbetween the first and second electrodes.

The first and second electrodes may be formed simultaneously, orsequentially.

In certain embodiments, the method also includes applying an electricalpotential to the first terminal, thereby creating an attractive forcebetween the first electroactive material and the first terminal. In atleast some such embodiments, particles of the first electroactivematerial are deposited at the first terminal.

In some embodiments, the second electroactive material has athree-dimensional structure defining a void space, and the repulsiveforce between the first and second electroactive materials causesparticles of the first electroactive material to concentrate in the voidspace. In certain embodiments, the second electroactive material is aporous electrode, and the repulsive force between the first and secondelectroactive materials causes particles of the first electroactivematerial to concentrate in the pore space of the porous electrode. Insome embodiments, the porous electrode is a reticulated open-cellcarbon, metal or ceramic foam.

In certain embodiments, particles of at least one of the first andsecond electroactive materials are coated with a conductive material.

Another aspect provides a method of making an electrode and an electrodemade according to the method. The method includes providing a firstterminal and providing conductive particles of an electroactive materialin a medium. The method further includes providing a second terminal. Anelectrical potential is applied between the first and the secondterminal to deposit conductive particles of the electroactive materialat the first terminal thereby forming an electronically continuouselectrode. A continuous bridge of conductive particles of theelectroactive material is formed between the first and second terminals.The applied electrical potential is removed.

In some embodiments, the method further comprises providing a thirdterminal and providing conductive particles of a second electroactivematerial in a medium. The method further comprises providing a fourthterminal and applying an electrical potential between the third and thefourth terminals to deposit conductive particles of the secondelectroactive material at the third terminal thereby forming a secondelectronically continuous electrode. A second continuous bridge ofconductive particles of the second electroactive material is formedbetween the third and fourth terminals. The applied electrical potentialis removed.

Another aspect provides a battery. The battery comprises a substrate, afirst terminal, a second terminal; and a localized conductive regioncomprising electroactive material formed on the substrate and surroundedby an insulating region. At least one of the first and second terminalsis electronically connected to the conductive region.

Other aspects, embodiments and features of the invention will becomeapparent from the following detailed description of the invention whenconsidered in conjunction with the accompanying drawings. Theaccompanying figures are schematic and are not intended to be drawn toscale. In the figures, each identical, or substantially similarcomponent that is illustrated in various figures is represented by asingle numeral or notation. For purposes of clarity, not every componentis labeled in every figure. Nor is every component of each embodiment ofthe invention shown where illustration is not necessary to allow thoseof ordinary skill in the art to understand the invention. All patentapplications and patents incorporated herein by reference areincorporated by reference in their entirety. In case of conflict, thepresent specification, including definitions, will control.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of depositing an electrochemicallyactive material using electrophoresis according to certain embodiments.

FIGS. 2A-B are schematic illustrations of the formation of layeredbattery configurations using electrophoretic deposition and simultaneousseparation according to certain embodiments.

FIG. 3 is a schematic illustration of a system for spatiallyconcentrating a cathode material in the pore space of a porous foamanode using electrophoresis according to certain embodiments.

FIG. 4A is a schematic illustration of spatially concentrating a cathodematerial in the pore space of a porous foam anode using electrophoresisaccording to certain embodiments. FIG. 4B is an expanded view of thefoam.

FIG. 5 is a top view of a microelectrode array deposited on glass, whichis useful for carrying out electrophoresis according to certainembodiments.

FIG. 6 is a chart showing a cyclic voltammetry scan of a heat treatedcarbon foam, tested in a Swagelok® cell against a lithium metal foilelectrode, showing reversible electrochemical insertion of lithium atthe expected potential for carbon anodes.

FIG. 7 is a chart showing cyclic voltammetry results from severalsamples of devices assembled by electrophoresis according to certainembodiments. Testing was performed at various scan rates between 0 and4.2V at room temperature. In each case, the sample resistance remainedhigh up to the maximum voltage, showing that electrical insulation waspreserved.

FIG. 8A is a top view of a microelectrode array with LiCoO₂ and Super P™carbon electrophoretically deposited at one electrode according tocertain embodiments.

FIG. 8B is a top view of a microelectrode array with LiCoO₂ and Super P™carbon electrophoretically deposited at one electrode and mesoporousmicrobeads (MCMB) electrophoretically deposited at the other electrodeaccording to certain embodiments.

FIG. 9 is a plot illustrating galvanostatic cycling (30 mA/g) vs.lithium metal of reticulated vitreous carbon, fired at 2400° C. in Hegas for 4 hours, showing low first-cycle irreversibility and lowcapacity fade to 10 cycles.

FIGS. 10A-C are plots of galvanostatic voltage-capacity curves at C/24rate for an electrophoretically assembled cell, calculated for LiCoO₂mass. FIG. 10A shows a first charge curve exhibiting large excesscapacity attributed to the reversal of electrochemical reactions inducedduring electrophoresis. FIG. 10B shows discharge curves for the firstfew cycles exhibiting similar voltage profiles, with the capacityvarying with upper voltage limit during charge. FIG. 10C shows the sixthcycle exhibiting polarization during charge and discharge of ˜0.2V aboutthe open circuit voltage.

FIGS. 11A-B are schematic illustrations of cell designs in which a canand a tab are used as working electrodes for electrophoretic forming,and subsequently are used as current collectors of the resultantbattery.

FIGS. 12A-B show a two-step deposition process for the electrophoreticassembly of a battery as described in Example 8.

FIG. 13 shows the charge and discharge for cycle number 40 for thebattery of FIGS. 12A and 12B as described in Example 8.

FIGS. 14A-B show a two-step process for making a battery byelectrophoretic deposition on a set of four electrodes as described inExample 8.

FIGS. 15A-C show the deposition from a mixture of 1 wt % LiCoO₂ inacetone at 2, 2.5 and 3 V, respectively, as described in Example 9.

FIGS. 16A-C show the deposition from a mixture of 1 wt % LiCoO₂ inacetone at 5 V as described in Example 9.

FIG. 17 shows a reticulated carbon foam attached to a second Pt meshcurrent collector, and placed above a first Pt mesh current collector asdescribed in Example 7.

FIG. 18 shows the current measured between two current collectors as afunction of time for two values of applied voltage as described inExample 7.

FIG. 19 shows a pattern of terminals having a serpentine configurationas described in Example 10.

FIG. 20 shows a pattern of terminals having a spiral configuration asdescribed in Example 10.

FIG. 21 illustrates configurations of terminals allowing depositioncorresponding to the method of Example 3 as described in Example 11.

FIG. 22 illustrates configurations of terminals allowing depositioncorresponding to the method of Example 8 as described in Example 11.

DETAILED DESCRIPTION

The invention provides methods of assembling bipolar electrochemicaldevices using electrophoresis. Electrical potentials and electric fieldsare used to form electrochemical junctions between positive and negativeelectrodes, and electrochemical devices are fabricated with a variety ofinternal designs or architectures, including one-, two-, andthree-dimensional constructions. By way of non-limiting example, methodsas disclosed herein are useful for making laminated devices, bobbinconstruction batteries and variants thereof, planar interpenetratingelectrode structures, and three-dimensional interdigitated andinterpenetrating structures, such as those based on the infiltration ofone porous electrode with an opposing electrode. Many such devicearchitectures are described in detail in U.S. patent application Ser.No. 10/206,662, published as US 2003/0099884 A1, which is incorporatedby reference herein. Non-limiting examples of device configurationssuitable for assembly by electrophoretic methods as described hereininclude a cell comprising a single pair of parallel linear electrodes, asingle planar cell stack consisting of a laminate having one positiveand one negative electrode, multiple laminates or multilayer stacks, atwo-dimensional array of alternating linear electrodes, atwo-dimensional interdigitated electrode array, a three-dimensionalarray of interdigitated electrodes, three-dimensional interpenetratingelectrode arrays, three-dimensional interpenetrating electrode arrays inwhich at least one electrode is in the form of an open-cell foam, asintered porous particle aggregate, a mat of fibers or ribbons, a weaveof fibers or ribbons, stacked mats or weaves of fibers or ribbons, andnon-interpenetrating or non-interdigitated cells in which at least oneelectrode is porous.

Methods of the invention are useful for assembling electrochemicaldevices including but not limited to batteries (of primary or secondarytype), capacitors, fuel cells, electrochromic displays and windows, andsensors. Advantageously, assembly of devices according toelectrophoretic methods as described herein does not require insertionof a discrete separator film or electrolyte layer, as is conventionallydone in the fabrication of electrochemical devices. Devices assembled asdescribed herein can be “separatorless” because an electronicallyinsulating, ionically conductive layer is formed in situ between theanode and cathode during electrophoretic assembly. Methods as describedherein are useful for assembling devices with lower manufacturing cost,higher energy density and power density, and longer cycle life thancomparable devices produced by conventional methods.

In at least some embodiments, electrophoretic assembly of a device iscarried out by applying an electrical potential between two electrodesthat subsequently are used as the terminals or working electrodes of thedevice. For example, in certain embodiments, electrophoresis is used todeposit a first electrochemically active material, and optionallyadditives, at a first electrode, current collector, or terminal of adevice. Electrophoresis is effected by applying an electrical potentialbetween the first electrode and a second electrode, current collector,or terminal of the device. The potential applied to the second electrodecauses it to repel the first active material. In at least someinstances, the first active material is also attracted to the firstelectrode. By applying an electrical potential between the two terminalsof the device, a physical separation is produced between the two activeelectrode materials without requiring the insertion of a discreteseparator film or electrolyte layer, as is conventionally done in thefabrication of electrochemical devices such as batteries, capacitors,fuel cells, and electrochromic devices. In at least some embodiments,electrophoresis is carried out in a fluid medium that remains betweenthe electrophoretically separated materials. In certain embodiments, bylimiting the volume available to the electrophoretically mobileparticles, a device is produced with very small diffusion distancesbetween electrodes.

In some embodiments, the second electrode of the device being assembledby electrophoresis is a terminal or current collector at which a secondactive material previously has been deposited, by electrophoretic orother means. In certain embodiments, the second electrode is itself madeup of a functional electrochemically active material. In some instances,the second electrode is assembled by electrophoresis simultaneously withthe first electrode, or sequentially before or after the firstelectrode.

FIG. 1 illustrates an exemplary arrangement for depositing electroactivematerials by electrophoresis, as described in more detail in Example 1below. As shown in FIG. 1, two parallel films of gold 10, 11 sputteredon glass are placed in a beaker 12.

A suspension 14 of electrophoretically mobile particulates 16 of one ormore materials is placed in the beaker 12. In the illustratedembodiment, the particulates are LiCoO₂, a lithium intercalation cathodeactive material for lithium ion batteries, and Super P™, a high surfacearea conductive carbon used in lithium battery electrode formulations. ADC power supply 18 is used to apply a voltage to the electrodes 10, 11.The voltage causes the particulates 16 to be repelled from one electrode10 and migrate toward, and eventually deposit on, the other electrode11.

Non-limiting examples of layered or laminated battery cells made usingelectrophoretic deposition and simultaneous separation are shown inFIGS. 2A-B. Referring to FIG. 2A, to carry out electrophoretic assembly,a voltage is applied between a sheet or mesh cathode current collector20 and an anode current collector 21, which is connected to a lithiummetal or carbon anode 22. A colloidal suspension 23 containing particlesof an intercalation compound 24, a polymer electrolyte 25, and a lithiumsalt (e.g., LiClO₄), with or without an organic solvent, is providedbetween the current collectors 20, 21. Upon application of voltage, theparticles of intercalation compound 24 are deposited to form anelectronically conducting network on the cathode current collector 20.The polymer electrolyte 25 is solidified, and forms a permanentseparator between the electrodes. Referring to FIG. 2B, a fluid mixtureof anode particles 26 in a molten polymer or polymer solution isprovided between an anode current collector 21, and a cathode currentcollector 20, which is connected to a cathode film 27. Upon applicationof a voltage across the current collectors 20, 21, the anode particles26 are deposited on the anode current collector 21, and an in situformed isolation layer 28 is created between the electrodes.

Non-limiting examples of suitable electrochemically active materials foruse in electrophoretic methods as described herein include ion storagematerials for assembling a battery, electrochromically active materialsfor assembling certain electrochromic devices, high surface area activematerials for assembling certain electrochemical capacitors, activematerials for hybrid battery-capacitor devices utilizing both Faradicand capacitive charge storage, and electrodes or catalysts for certainfuel cell assemblies. Useful additives include but are not limited toconductive particles that increase the electrical conductivity of thedeposited material, such as conductive carbon, metallic particles, orconductive polymer dispersions, or binders that improve the adherence ofthe deposited particles to each other or to a current collector.

Suitable materials for electrophoretic assembly are identified by theirability to meet a desired function in the subject electrochemicaldevice. For example, in a rechargeable lithium ion battery, anintercalation oxide able to reversibly store lithium at a high potentialwith respect to lithium metal is useful as the active material at thepositive electrode. Such materials are well-known to those havingordinary skill in the art, and include ordered-rocksalt compounds suchas LiCoO₂, LiNiO₂, Li(Al, Ni, Mn)O₂, LiMnO₂, and solid solutions ordoped combinations thereof; spinel structure compounds such as LiMn₂O₄and its doped counterparts or solid solutions with other metal oxides;ordered olivines such as LiFePO₄, LiMnPO₄, LiCoPO₄, and their dopedcounterparts or solid solutions; and other ordered transition metalphosphates such as those of so-called Nasicon structure type and theirderivatives and related structures. For the active material at thenegative electrode of a lithium-ion battery, examples of suitablecompounds include compounds such as graphitic or disordered carbons;metal oxides that intercalate lithium such as Li₄Ti₅O₁₂ spinel and itsderivatives; and other metal oxides or their solid solutions thatundergo intercalation or displacement reactions such as tin oxide,indium tin oxide, or first-row transition metal oxides; and crystallineor amorphous metals and alloys of metals or metalloids such as Si, Al,Zn, Sn, Ag, Sb, and Bi. For a primary battery, suitable electrode-activematerials include without limitation those well-known to those ofordinary skill in the art to form useful electrochemical couples, suchas Zn and MnO₂ in the case of the aqueous Leclanche oralkaline-manganese cells, zinc and mercuric oxide in the case of a“mercury cell,” or lithium and copper oxide or lithium and manganeseoxide in the case of primary lithium batteries. For an electrochemicalcapacitor or hybrid battery-capacitor, useful electrode materialsinclude without limitation high surface area carbons or metal oxides.For an electrochromic displaying or transmitting device, useful activematerials include but are not limited to transition metal oxides andother chromophoric compounds that change color or optical transmissionupon being electrochemically oxidized or reduced. For a fuel cellmembrane assembly, useful active materials include without limitationconductor and catalyst particles serving as the positive or negativeelectrode.

Materials and materials combinations for electrophoretic assembly arealso selected by the direction and rate at which they migrate under anapplied electric field. Electrophoresis can be effected for chargedentities of widely ranging sizes, as large as particulates manymicrometers in size or as small as individual molecules and ions. In aliquid medium, charged particles and molecules have an electrophoreticmobility whose sign is given by the direction of motion, and whosemagnitude is given by the velocity of the entity under a given magnitudeof electric field. Methods for determining electrophoretic mobility arewell-known to those having ordinary skill in the art of colloids, powdermaterials processing, or surface chemistry. For many materials dispersedin aqueous or nonaqueous media, the zeta potential, which is defined asthe electrical potential at a dividing plane separating electricalcharge that is fixed to the solid and that which is freely mobile in thefluid, is tabulated or can be predicted or can be measured by standardmethods. The sign and magnitude of the surface charge on particularmaterial particles can be selected or altered in a number of wayswell-known to those having ordinary skill in the art, including but notlimited to varying the solvent or solvents, pH of the suspension,concentration of added salts, or by adding various charged molecules orsurfactants that adsorb to the particle surface. As shown herein, thezeta potential can also be controlled by varying the magnitude of theapplied voltage between the electrodes effecting deposition, such thatat a low voltage the zeta potential has one value, and at a highervoltage the zeta potential has a different value or even a differentsign. The voltage at which the sign of the zeta potential may changediffers for different solvents or mixtures of solvents and dissolvedsalts or organic species, and can also be determined through methodswell-known to those skilled in the art. One or more of these factors areemployed in order to select the materials and solvent system forelectrophoresis. The rate of deposition of particles at a particularelectrode is determined by controllable experimental variableswell-known to those of ordinary skill in the art, including but notlimited to the magnitude of the voltage and the electric field, theparticle concentration in suspension, magnitude of the zeta potential,size and shape of the particle, and viscosity of the medium. Asillustrated in Example 1 below, direct observation of the direction ofmotion and rate of deposition of a desired particulate material underelectric field is readily performed, and is an effective means ofscreening or selecting materials and materials combinations.

In some embodiments, the particles undergoing electrophoretic migrationare coated with a conductive material that optionally also determinesthe zeta potential or electrophoretic mobility of the particles.Suitable coatings include carbonaceous materials; conductive oxides,including but not limited to indium tin oxide, doped tin oxides, anddoped zinc oxides; and conductive polymers. Conductive polymer coatingsare useful for providing high electronic conductivities, adequatelithium ion diffusivity, and lower elastic modulus, such that uponcontact the contact points are deformable, resulting in greater contactarea between particles and greater electronic conductivity for theelectrophoretically concentrated network. Suitable polymers include, forexample, commercially available conductive polymers such as Baytron® P(Bayer AG, Leverkusen, Germany), poly3,4-ethylenedioxythiophene/polystyrenesulfonic acid complex, andconductive polymers described in U.S. patent application Ser. No.10/876,179, published as US 2005/0034993 A1, which is incorporated byreference herein. Some such polymers have electronic conductivity of atleast about 1 S/cm, and as high as about 75 S/cm. In some instances, theconductive component includes one or more groups selected frompolyaniline, polypyrrole, polyacetylene, polyphenylene, polythiophene,polyalkylenedioxythiophene, and combinations thereof. In certainembodiments, the conductive polymer includes one or more groups selectedfrom Structures I-V:

wherein Rf is a fluorinated alkyl group, aryl group, or combinationthereof, X is a linking group attaching Rf to the polymer backbone, andR is a pendant group chosen from X-Rf, H, and methyl. In someembodiments, X includes one or more groups selected from alkyl, ether,thioether, ester, thioester, amine, amide, and benzylic groups. In someembodiments, the polymer includes one or more groups selected fromEDOT-F (pentadecafluoro octanoic acid2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-ylmethyl ester), Th—O-1,7(3-pentadecafluorooctyloxythiophene), Me-Th—O-1,7(3-methyl-4-pentadecafluorooctyloxythiophene), and PrODOT-F(propylenedioxythiophene pentadecafluorooctane ester).

In at least some embodiments, the mode of electrophoretic deposition isdetermined by varying the composition of the particle suspension fromwhich deposition occurs, the dimensions and separation of theelectrodes, and/or the applied voltage. In certain embodiments, the“mode” of electrophoretic deposition includes one or more of thefollowing. In one mode, highly conductive particles that, upondeposition, form a continuous network of conductive particles, have theeffect of extending the conductive electrode at which deposition occurs.The electric field causing deposition is determined by the appliedvoltage, and the separation between the electrodes. This mode ofdeposition is susceptible to the formation of locally increased electricfield where particles deposit. This in turn increases the depositionrate, leading to an instability of the deposited layer, which causes theformation of branches or “dendrites.” Such dendrites can subsequentlylead to a continuous bridge between electrodes, causing an electricalshort circuit, especially when the electrodes are closely spaced inrelation to the thickness of the desired deposit (for example, anelectrode spacing less than about five times the thickness of thedeposited layer, if deposited uniformly). In certain embodiments, thismode of electrophoretic deposition is used to practical advantage, tocontrol the location and amount of electrodeposited active material. Inat least some such embodiments, a pair of deposition electrodes is usedto create each final electrode.

When the deposited particles are largely insulating, the mode ofdeposition generally differs from the previous one, in that thedeposited particles do not cause significant increase in the electricfield through the narrowing of the electrode gap. In this mode, referredto as “plating,” the deposited layer of particles typically remainsrelatively uniform in thickness as the particles deposit. Another, modeof deposition that results in a uniform thickness of deposit occurs whenthe electrophoretic velocity of the particles is sufficiently greaterthan the diffusional velocity of the particles. In this mode, theparticles are deposited before they have an opportunity to diffuselaterally under Brownian motion to an extent allowing the formation ofdendrites, and the deposit is typically uniform. This mode generallyoccurs under high electric fields, e.g., for closely spaced electrodesand/or high applied voltages, and the particles deposited are primarilylimited to those present between the electrodes when the field isinitially applied. A certain extent of dendrite formation is allowablebefore electrical shorting between the electrodes occurs. The ratio ofelectrophoretic velocity to diffusional velocity necessary to preventshorting due to dendrite formation depends on the density of particlesin the suspension, the thickness of the deposit, the electrode geometryand the spacing of electrodes, amongst other factors, and is readilydetermined by direct experimentation.

Yet another mode of deposition typically occurs under high appliedvoltage in electrolytic solutions. It was surprisingly observed that thebridging phenomenon leading to electrical shorting between depositionelectrodes can be avoided when the applied voltage is sufficientlylarge, greater than about 5 volts and preferably about 10 volts. In thiscase, even closely spaced electrodes or deposits do not electricallyshort, and a densely packed electrode system is facilitated. Since ourdiscovery, similar observations of this phenomenon during theelectrodeposition of carbon nanotubes have been reported by Kamat etal., J. Am. Chem. Soc. 126:10757-10762 (2004). In another embodiment,electrical shorting between electrodes is prevented by providing inliquid suspension or solution other constituents that are electronicallyinsulating and deposit more quickly than the electronically conductiveactive materials. Such constituents include, for example, a polymer orother organic material, components of a dissolved lithium salt, or areaction product formed at the electrode surface upon theelectrodeposition of such a constituent. The reaction product resultsfrom a reaction between the deposited constituent and anotherconstituent of the suspension, or between the deposited constituent andthe electrode material itself, such as a lithium carbonate forming onthe surface of a carbon electrode.

In at least some embodiments, selection of a separator or electrolytematerial that remains between the electrophoretically separatedmaterials is carried out in the following manner. The separator materialis electronically insulating. In some embodiments, the separator isitself an ion-conducting electrolyte, or is rendered ionicallyconducting after electrophoretic separation, for example, by infusingwith an electrolyte. Suitable separator materials include organic,inorganic, and organic-inorganic hybrid materials. By way ofnon-limiting example, to create a solid polymer electrolyte in a finaldevice, a solvent such as acetonitrile is selected, in which thefollowing are soluble: a polymer that is the basis for a solid polymerelectrolyte, such as polyethylene oxide (PEO); and a lithium salt thatdissociates in the polymer and renders it ionically conducting, such asLiClO₄. Many such lithium salts are known to those of ordinary skill inthe art. After electrophoretic separation and drying, a LiClO₄-doped PEOsolid electrolyte remains.

In certain embodiments, electrophoretic separation is conducted in thepolymer electrolyte itself, at an elevated temperature where it ismolten. That is, the molten electrolyte is the liquid solvent. Afterseparation is conducted at elevated temperature, the device is cooled toa lower temperature to preserve the structure. In such embodiments,operation of the device takes place at a temperature equal to or lowerthan the electrophoretic separation temperature.

In some embodiments, the separator is a material that is cross-linked orotherwise rendered rigid during or after electrophoretic separation. Forexample, a polymer that is UV-curable or chemically curable orthermosetting is used as the liquid medium, optionally with a solvent.Polymerization is effected during or after electrophoretic separationhas occurred. In some instances, the separator is a binder material thatis not itself ionically conductive, but is infused with electrolyteafter separation. As a non-limiting example, for a non-aqueous battery,a polymer binder such as polyvinylidine fluoride (PVDF) is dissolved ina compatible solvent, such as acetone or N-methyl pyrrolidinone (NMP) orgamma-butyrolactone, forming a solution in which electrophoreticseparation is effected. Following drying, the device is infused with anorganic liquid electrolyte. Such porous or infusible binders alsoinclude inorganic substances such as a sol-gel derived oxide, or anorganic-inorganic hybrid.

In addition to the electrophoretic deposition of materials, in certainembodiments the electrochemical deposition of materials from a fluidmedium is also used. For example, in some instances metal or salt ionsin liquid solution are deposited under applied electrical potential inorder to deposit an ion storage compound or conductive additive at anelectrode of an electrochemical device. In certain embodiments, theelectrophoretic deposition of particles or electrochemical deposition ofcompounds is increased by replenishing the fluid medium duringdeposition, for example by repeated infiltration by the fluid oreffecting continuous flow of the fluid through the device undergoingdeposition.

In certain embodiments, electrical potential is applied to repel a firstactive material (and optionally additives having the same sign ofelectrophoretic mobility) from a second electrode that has athree-dimensional structure defining a pathway or void space therein.The electric field repels the first active material from the secondelectrode, thereby concentrating the first active material in the voidspace of the second electrode. In at least some such embodiments, theprocess of electrostatic repulsion substantially densifies the firstactive material, causing it to form an electrically continuouselectrode. This continuous electrode, electrically connected to a firstterminal or current collector, is then the first electrode of thedevice. By limiting the volume available to the electrophoreticallymobile particles, a densely packed network of the first active materialis formed, while electrical separation is maintained between the twoelectrodes.

In some instances, the second electrode is a porous electrode. Incertain embodiments, the porous electrode is a reticulated open-cellfoam. Such foams are available in materials including carbon, variousmetals and ceramics. These materials are easily machined into arbitraryshapes, useful for fabricating batteries of complex nonstandard formfactors. One non-limiting example of a useful porous electrode is acontinuous carbon structure having substantial open porosity, such as acarbon foam or carbon fiber mat. In particular embodiments, a carbonfoam is used as an anode network to form a three-dimensional lithium ionbattery. The pore space within the carbon foam is infiltrated with acathode particulate network that is electrophoretically separated fromthe carbon structure to form the device. In specific embodiments, thecarbon anode foam is infiltrated with a suspension containing a cathodeactive material, a polymer, and optionally additives. The cathodesuspension is infiltrated into the anode carbon foam at elevatedtemperature. An electrical potential is applied so that the cathodematerial is repelled from the anode foam. Because the cathode suspensionresides in a confined volume and cannot exit the sample, the particlesare electrophoretically concentrated in the pore space of the foam,forming a continuous, interpenetrating network of the positive electrodematerial. This electrophoretically separated structure is fixed bycooling the system to solidify the polymer while still applying theelectrical potential. In some alternative embodiments, the cathodesuspension contains a solvent, and the structure is fixed by drying thesolvent, rather than heating and subsequent cooling of the polymer. Insome embodiments, the infiltration of the porous electrode by thesuspension is expedited by carrying out infiltration with a pressuregradient across the porous electrode, or by applying a vacuum to aporous electrode immersed in a suspension, thereby removing trapped gasin the porous electrode. In certain embodiments, the drying of theinfiltrated porous electrode is expedited by heating, application ofvacuum, or both.

FIGS. 3 and 4 illustrate an exemplary arrangement for athree-dimensional concentrating electrophoretic method using a carbonfoam anode, as described in more detail in Example 2 below. Referring toFIG. 3, a carbon foam anode 30 is connected to a copper currentcollector 32, and a cylindrical container 34 is placed around the foam30. A suspension 36 containing polymer and cathode material is pouredinto the container 34 and allowed to infiltrate the foam 30. An aluminumcurrent collector 38 is connected to the cathode suspension 36 withoutcontacting the foam 30. In some alternative embodiments, the currentcollector 38 is another suitable material, such as platinum, instead ofaluminum. A voltage is applied between the copper 32 attached to thefoam 30 and the aluminum current collector 38, with the aluminum currentcollector 38 at negative potential and the copper 32 at positivepotential. Upon application of the voltage, as shown in FIG. 4, cathodeparticles 40 are concentrated into the pore space 42 of the foam 30.Simultaneously the cathode suspension 36 is electrophoreticallyattracted to the upper current collector, where it forms a goodelectrical contact. This process can be directly monitored by observingcurrent flow between the current collectors; electrical isolationbetween the two electrodes is seen as the decay of current to negligiblevalues. Upon cooling (or otherwise solidifying the polymer), theelectrophoretically separated configuration is fixed in the finaldevice.

In some alternative embodiments, a liquid electrolyte cell is prepared.In this case, a solvent is employed, for example, that can dissolvepolymer binders or gel network formers. To complete the electrochemicalcell, the electrophoretically separated system is dried and infiltratedwith a standard liquid electrolyte. Since most particulate materials canbe induced to have a surface charge in appropriate liquids, thisapproach is applicable to a wide range of active materials. Theidentification of a suitable system is illustrated in Example 4 below.Exemplary alternative arrangements for a three-dimensional concentratingelectrophoretic method using a reticulated foam electrode include thosedescribed in Example 6 below. In some alternative embodiments, thestationary porous network is the positive electrode material, and theinfiltrant a suspension of negative electrode material.

In certain embodiments, electrophoretic methods are used to producedevices in which it is desirable to have a high volume fraction ofactive materials, e.g., storage batteries. In at least some suchembodiments, due to electrophoretic assembly, the volume availablewithin the fabricated device is predominantly occupied by the activematerials, with only a minority of the volume occupied by a fluid phase.As a non-limiting example, a device is assembled using a suspension ofparticles of a first active material in a fluid phase or phasesincluding a binder or a polymer electrolyte, optionally combined with asolvent. Electrophoretic separation is effected by applying anelectrical potential between first and second electrodes or terminals ofthe device, causing the second electrode to repel the particles of thefirst active material. In some embodiments, particles are deposited atone electrode, and an insulating layer Of material is electrodepositedat the opposite electrode. The electrophoretically separated devicestructure is preserved, for example, by cooling the device, removing thesolvent by drying, or crosslinking the binder or polymer by thermal,chemical, or radiative means (e.g., using a UV crosslinkable polymer)while still applying the electric potential. In this manner, a thin butelectronically insulating separation is obtained between the twoelectrodes. Electrochemical function is then available, or becomesavailable upon infusion of an electrolyte into the device. Theelectrolyte infuses the space between the electroactive materials, andin at least some instances also infuses pore space within theelectroactive materials. When a binder is present between theelectroactive materials, the electrolyte infuses the available porespace unoccupied by the binder, and in at least some instances ispartially absorbed by the binder itself.

The electrophoretic assembly methods described herein are especiallyuseful for fabricating three-dimensional interpenetrating devicearchitectures, in which reliable electrical separation between two highsurface area interpenetrating electrodes can be difficult to achieve.Such structures include, but are in no way limited to, the porous foamelectrode structures described in Example 2 below. Electrophoreticassembly as described herein provides an alternative to coating theinternal surfaces of an anode foam with a thin layer of a separatormaterial, and then infiltrating the remaining pore space with a cathodeparticulate suspension, as described in U.S. patent application Ser. No.10/206,662, published as US 2003/0099884 A1.

Electrophoretic assembly methods as described herein are also useful inproducing standard battery architectures. By way of non-limitingexample, primary batteries of cylindrical form factor typically have abobbin construction, in which the anode (e.g., made of powdered zinc) isa central post, and the cathode (e.g., made of manganese oxide and otherconstituents) forms an outer bobbin. According to conventional methods,a continuous sheet of porous separator film is used to isolate thecathode and anode, and the whole is infused with aqueous electrolyte.Electrophoretic methods according to certain embodiments are useful forfabricating such batteries more simply and economically, to yield a cellhaving a greater volume fraction of storage materials, and thereforehigher energy, than cells produced by conventional techniques.

In one embodiment, a battery of cylindrical form factor having a bobbinconstruction is assembled using electrophoresis. The battery has acentral anode that serves as one working electrode for carrying outelectrophoretic separation. A can housing the battery is filled with asuspension of cathode active material in a solvent that also contains apolymer solution or dispersion. A potential is applied so that thecathode active material is repelled from the central anode post andconcentrated by electrophoretic forces. This repulsion and concentrationof the cathode material causes the formation of a gap between the anodeand cathode, which is filled by the solvent and polymer. The solvent isallowed to dry, and the polymer deposits between the anode and cathode,so that the anode and cathode remain electrically isolated without theuse of a separate separator film. In some instances, the polymer alsodeposits within the electrodes and acts as a binder. The polymer and theformulations used are selected by methods well-known to those ofordinary skill in the art for leaving behind a porous separator layer.The battery is then infused with liquid electrolyte.

The following non-limiting examples further illustrate certainembodiments.

Example 1

The direction of electrophoretic migration was determined for severalmaterials and solvent systems useful in batteries as follows.Measurements were made of the direction of motion of powders suspendedin solvents between two gold working electrodes under an appliedvoltage. The gold electrode configuration was one of the following: (1)as shown in FIG. 1, two parallel films of gold 10, 11 sputtered on glassplaced ˜0.5 cm to ˜1 cm apart in a small glass beaker 12 (20 ml or 30ml) in which the suspension 14 was placed, (2) two sputtered goldelectrode films 1 cm apart in a glass plate with a shallow well withinwhich the suspension was placed, or (3) as shown in FIG. 5, individuallyaddressable gold microband electrodes 50 (ABTECH Scientific, Richmond,Va.) deposited on glass, typically of 20 micron width and 20 micronseparation, onto which a suspension was placed. For the microbandelectrodes, the polarity alternated between bands.

A powder suspension was prepared by placing the powder or powders ofinterest into a solvent, typically at a concentration of 1 mg of solidpowder per 1 ml of solvent. A constant voltage (typically 3-10V) wasapplied to the electrodes, and then the suspension was placed intocontact with the electrodes. After 10 min. to 30 min. for the first twoelectrode configurations, and 30 sec. to 5 min. for the microbandelectrodes, the deposition of powder was observed in order to determinethe direction of electrophoretic migration. This allowed the subsequentselection of solid and solvent/polymer systems.

The solid powders tested included LiCoO₂ (Alfa-Aesar, Ward Hill, Mass.),mesoporous microbeads (MCMB) (Osaka Gas Co., Japan), Super™ carbon(Timcal, Belgium), indium tin oxide (ITO) powder (Aldrich Chemical,Milwaukee, Wis.), and doped lithium iron phosphate from A123Systems(Boston, Mass.).

The pure solvents and solvent mixtures tested included the following:

-   -   1) acetonitrile    -   2) acetone    -   3) isopropanol    -   4) dimethyl formamide    -   5) acetonitrile with dissolved polyethylene glycol (PEG,        1500-8000 molecular weight) or polyethylene oxide (PEO, 200,000        MW) and LiClO₄    -   6) acetone with dissolved polyvinylidine fluoride (PVDF, 534,000        MW) and LiClO₄.

The following migration directions were observed. LiCoO₂ migrated towardthe positive electrode in solvents 1 and 2, and toward the negativeelectrode in solvents 4, 5 and 6. MCMB migrated toward the positiveelectrode in solvent 2, and toward the negative electrode in solvents 1,4, 5, and 6. Super™ migrated toward the positive electrode in solvent 2,and toward the negative electrode in solvents 1, 5, and 6. ITO migratedtoward the positive electrode in solvents 1, 2, and 5, and toward thenegative electrode in solvent 3. LiFePO₄ migrated toward the negativeelectrode in solvent 5.

Experiments were also conducted to observed the direction ofelectrophoretic migration and deposition for several polymers commonlyused in lithium ion battery systems. In pure acetone, polyvinylidenefluoride (PVdF) having a molecular weight of 60,000 (Polysciences Inc),and Kynar 461, a PVdF homopolymer (Atofina) were both observed todeposit on the positive electrode, indicating existence of a negativezeta potential. When LiClO₄ salt was added to acetone, however, theKynar 461 did not exhibit migration under electric field, indicatingthat the zeta potential is readily compensated. Kynar 2801, a PVdF-HFPcopolymer (Atofina) did not exhibit electrophoretic migration even inpure acetone, indicating negligible zeta potential. This demonstratesthat combinations of materials can be readily selected in which apolymer constituent as well as particles of inorganic active materialsare electrophoretically deposited or not. Electrodeposition of a polymercan serve useful functions such as being a binder for other particles orto provide an electronically insulating layer or “in-situ” separatorlayer.

These results allow for the selection of single materials orcombinations of materials that will migrate to or from a given electrodeunder a certain applied voltage. For example, in solvent 5, which upondrying forms a solid polymer electrolyte, LiCoO₂ and Super P™ (as aconductive additive) migrate in the same direction, and can beco-deposited or co-aggregated to form an electrode. FIG. 1 illustratesthe obtained result of LiCO₂ and Super P™ 16 co-depositing at oneelectrode 11. The same can be done with LiFePO₄ and Super™ in solvent 5.The same co-deposited electrodes (LiCoO₂ and Super p™, LiFePO₄ and SuperP™) can be formed in solvent 6. In this instance, the solution ofsolvent with PVDF and LiClO₄ (or solvent and PVDF alone) will dry toform a binder that can be infused with a liquid electrolyte.

Examples of layered or laminated battery cells made usingelectrophoretic deposition and simultaneous separation are shown inFIGS. 2A-B. As illustrated, in FIGS. 2A-B, electrophoretic deposition ofLiCoO₂ and Super P™ at one electrode can be used to simultaneouslycreate an insulating gap between that electrode and thecounterelectrode, which in this example is a lithium foil or carbonelectrode, both selected to be capable of accepting lithium from theLiCoO₂ when the resulting cell is charged.

Example 2

This example demonstrates the assembly of an electrochemical deviceusing a continuous carbon structure having substantial open porosity,such as a carbon foam or carbon fiber mat, as one working electrodeduring electrophoretic processing. This porous electrode also becomes aworking electrochemical storage electrode in the final device, which isa three-dimensional lithium ion battery.

In one series of experiments, reticulated carbon foams (Duocel™, ERGMaterials and Aerospace, Oakland, Calif.) having pore dimensions ofbetween 45 pores-per-inch (ppi) and 100 ppi were used. In some cases,the carbon foam was fired to high temperature (2300° C. to 2400° C.) inhelium in order to improve the electrochemical storage capability. FIG.6 shows a cyclic voltammetry scan of a heat treated carbon foam, testedin a Swagelok® cell against a lithium metal foil electrode, showingreversible electrochemical insertion of lithium at the expectedpotential for carbon anodes.

The pore space within the carbon foam was then infiltrated with acathode particulate network that was electrophoretically separated fromthe carbon structure in order to form the device. A cathode suspensionwas prepared from LiCoO₂, Super P™, acetonitrile, PEG or PEO, andLiClO₄. One typical formulation used was 5 ml acetonitrile, 0.6 gLiClO₄, 2.12 g PEG 1500, 3.2 g LiCoO₂, and 0.16 g Super P™.

FIG. 3 illustrates the configuration that was used for electrophoreticassembly. A cylindrical piece of foam 30 ˜16 mm in diameter by ˜10 mm inheight was attached to a copper current collector 32 with goodelectrical contact. A cylindrical container 34 (polypropylene or Teflon®(polytetrafluoroethylene, DuPont, Wilmington, Del.)) was placed aroundthe foam. The cathode suspension 36 was mixed uniformly, poured into thecontainer 34, and allowed to infiltrate the foam 30. The container 34was filled with a sufficient volume of the cathode suspension 36 to fillthe foam 30, leaving some excess to which an aluminum foil currentcollector 38 was connected at the top of the sample without contactingthe carbon foam 30. Cross-sections of an infiltrated sample showedpenetration throughout the foam 30 by the LiCoO₂ and Super R™.

A 10V potential difference was applied between the copper 32 attached tothe carbon foam 30 and the aluminum current collector 38. The aluminumcurrent collector 38 was at negative potential and the copper 32 atpositive potential. The sample was placed in a vacuum oven and heated to100° C., at which time a vacuum was applied to speed up drying of thesample. The current between the two electrodes was observed, and decayedto negligible values. The sample was then cooled to room temperature andremoved from the oven.

After cooling, the dc resistance between the copper and aluminum currentcollectors 32, 38 was >20 Mohms (measurable value being limited by themultimeter used). As shown in FIG. 4A, the LiCoO₂ and Super P™particulates 40 were electrophoretically repelled from the carbon anode30 and attracted towards the aluminum current collector 38, but remainedtrapped within the porosity 42 of the foam 30. Thus, the cathode activematerial 40 and the anode network 30 were electrophoretically separatedfrom one another. FIG. 4B shows an expanded view of the infiltratedfoam.

Cyclic voltammetry (CV) was performed to further demonstrate that thecathode and anode remained electrically isolated up to high voltagescharacteristic of lithium ion battery systems. FIG. 7 shows CV resultsfrom several samples tested at various scan rates between 0 and 4.2 V atroom temperature. In each case, the sample resistance remained high upto the maximum voltage, showing that electrical insulation waspreserved. FIG. 7 also shows CV results for a sample made using asuspension containing LiFePO₄ and Super P™ as the solid phases,demonstrating that electrical isolation was achieved using thissuspension as well.

Example 3

A two-dimensional electrophoretically separated device was fabricatedusing the following procedure. A 20 micron width microelectrode array 50deposited on glass (ABTECH Scientific, Richmond, Va.) as shown in FIG. 5was used. A suspension of LiCoO₂ and Super P™ powder in acetonitrile,PEO 200,000, and LiClO₄ was prepared using the same ratios as in Example2, and the suspension was then further diluted with additionalacetonitrile. The suspension was applied to the microelectrodes and a 1volt potential difference was applied to the array. As shown in FIG. 8A,deposition of the LiCoO₂ and Super™ 80 at the negative electrodes 82 wasobserved, with no detectable deposition at the positive electrode 84.

Next, a suspension of MCMB in the same solvent mixture was applied, withthe voltage being applied as shown in FIG. 8B. MCMB was found, likeLiCoO₂ and Super P™, to migrate to the negative electrode in thissolvent mixture. Therefore, in order to deposit MCMB 86 at the oppositeelectrode 84 from the LiCoO₂ and Super P™ 80, the voltage was reversedfrom that used to deposit the LiCoO₂ and Super P™ 80. It was observedthat MCMB 86 deposited at the opposite electrode 84 from the LiCoO₂ andSuper™ 80 as expected.

After deposition and drying, electrical measurements showed a >20 Mohmresistance between the two deposited electrodes. Thus, electrophoresiswas used to fabricate a two-dimensional battery array consisting ofinterpenetrating electrode structures, with electrical isolation betweenthe two. The intervening space between the electrodes can be filled withPEO and LiClO₄ solid polymer electrolyte, or infused with liquidelectrolyte.

Example 4

As in Example 2, a Duocel™ non-graphitizing reticulated vitreous carbonfoam was used as a stationary electrode. The foam had linearpore-per-inch (ppi) counts of 45, 60 and 100, and a bulk density of 0.05g/cm³. The as-received reticulated carbons were heat treated in agraphite resistance-heated furnace (Astro Corp., Santa Barbara, Calif.)at 2400° C. for 4 hours in He gas in order to improve their lithiumstorage capacity. A copper current collector was attached to acylindrical sample of the reticulated carbon (16 mm in diameter by 10 mmin height), forming a negative electrode structure that was placedwithin a close-fitting polypropylene container. Aluminum foil orplatinum mesh was used as a working electrode/current collector on thepositive electrode side, as illustrated in FIG. 3. The cell wasinfiltrated with a suspension of cathode active material, LiCoO₂ andSuper P™ carbon, in binder and solvent. After infiltration, whichoccurred on the time scale of seconds to minutes, a voltage of 10 voltswas applied across the two current collectors to effect electrophoreticseparation of the cathode active material from the stationary anode, asillustrated in FIG. 4. To complete the electrochemical cell, theelectrophoretically separated system was dried and infiltrated with astandard liquid electrolyte.

Cell balancing was then taken into account in selecting a specificsuspension formulation. The LiCoO₂ concentration in the suspension waschosen to yield a slightly cathode-deficient composition in the finalcell, i.e., one in which the lithium ion source is cathode-limited, inorder to avoid lithium metal precipitation at the negative electrodeduring charge. A typical suspension formulation in weight percentage was69.3% acetone, 3.5% LiClO₄, 8.7% PVDF (66,000 MW), 17.3% LiCoO₂, and1.3% Super P™. Taking the components of the electrode formulation alone,the weight proportions were 31.8% PVDF, 63.5% LiCoO₂, and 4.8% Super P™,which is binder-rich compared to typical cathode formulations, butuseful for cell balancing.

Cell infiltration and electrophoretic forming was conducted as follows.A quantity of the LiCoO₂ suspension sufficient to completely infiltratethe anode framework and contact the upper working electrode was pouredinto the cell. The cell was placed in a vacuum chamber at roomtemperature, and evacuated to facilitate infiltration of the suspensioninto the reticulated carbon. After infiltration, a 10V dc voltage wasapplied across the two current collectors. Due to the positive zetapotential of the particles, the negative potential appears at thecurrent collector to which the LiCoO₂ and Super P™ are attracted (FIGS.3 and 4). Relative to the final operation of the lithium ion battery,this is the polarity used for discharging. The large overpotentialresults in an initially “overdischarged” state of the cell, as shownbelow. The infiltrated cell was held at 10V de voltage for a total of 6hours, the first 2 hours at room temperature, and the following 4 hoursat 45° C. to complete drying. During electrophoretic forming, thecurrent dropped to <4 mA over a period of about 2 hours, and afterdrying, the dc resistance between the current collectors afterelectrophoretic forming was >10 MΩ. Control experiments conductedwithout the applied voltage showed complete electrical shorting betweenthe current collectors, confirming that the electrical isolation was dueto electrophoresis. Upon drying, the space between the positive andnegative electrodes was occupied by the PVDF binder, acting as a porousseparator. The cell was then flooded with liquid electrolyte (1:1ethylene carbonate:diethyl carbonate (EC:DEC) mixture with 1 M LiPF₆) inan argon-filled glove box, and subjected to electrochemical testing.

Electrochemical test results were carried out for the reticulated carbonin a Swagelok® design lithium half-cell. The as-fired reticulated anodewas crushed in a mortar and pestle and formulated with PVDF binder as anelectrode coating, then assembled in the cell using lithium metal foilas the counterelectrode and Celgard® 2400 (Celgard Inc., Charlotte,N.C.) as the separator membrane. FIG. 9 shows galvanostatic testing at30 mA/g current rate between 0 and 2V. The first-cycle irreversiblecapacity loss of the carbon was extremely low, and there was only ˜4%capacity fade over 10 cycles. Due to the half-cell configuration, anylithium consumed in passivating the carbon was not detected, but wouldbe present (several percent first cycle capacity loss) in a lithium-ionconfiguration. The carbon gravimetric capacity of 120 mAh/g wasconsiderably less than that of optimized graphite anodes (typically ˜350mAh/g). The lithium storage capacity of carbons is known to vary widely;in this instance the lower capacity may have been due to the densenature of the amorphous carbon and the relatively thick cross-section ofthe struts in the reticulated structure of about 50 μm. This may be toolarge a cross-section to allow complete lithiation at the current ratesused. For comparison, the particle diameter of a typical optimizedgraphitized MCMB (mesocarbon microbeads) anode is less than 25 μm.Nonetheless, taking the gravimetric capacity of the carbon to be 120mAh/g, the LiCoO₂ suspension was formulated to provide a cathode-limitedcell. The reticulated carbon samples used had a mass of ˜0.1 g,providing a capacity of 12 mAh. The LiCoO₂ suspension compositionyielded, after infiltration and drying, a cathode active massinfiltrated within the reticulated foam of ˜0.072 g. Given a typicalLiCoO₂ gravimetric capacity of 140 mAh/g, the positive electrodecapacity was then 10.1 mAh.

The first galvanostatic (C/24 rate) charge-discharge cycle of acompleted cell is shown in FIG. 10A. The open circuit voltage of thecells after assembly and drying, and even after filling by electrolyte,was negative (˜−1V after filling). Upon charging however, the potentialimmediately became positive, as seen in FIG. 10A. The first-charge curve(to 4.1V) was noisy and exhibited a larger capacity (275 mAh/g based oncathode active mass) than could be provided by the LiCoO₂ present. Inthe first discharge, however, the voltage profile was typical for aLiCoO₂/carbon couple, exhibiting an average voltage of ˜3.8V, andshowing a discharge capacity that when evaluated on the basis of theLiCoO₂ mass infiltrated into the cell was ˜100 mAh/g. The firstdischarge capacity in lithium ion cells is always lower than the firstcharge capacity due to coulombic inefficiencies such as irreversibleconsumption of lithium in forming the solid-electrolyte interphase (SEI)on the carbon, and other side reactions. Nonetheless, the observeddischarge capacity shows that at least 70% of the infiltrated LiCoO₂ waselectrochemically accessible.

FIG. 10B shows discharge curves for the first few cycles exhibitingsimilar voltage profiles, with the capacity varying with upper voltagelimit during charge. The first and second cycles were charged to 4.1Vlimit, and the third cycle to 4.2V. The sharp drop in voltage near theend of discharge for the second and third cycles was due to incompletecharging during their respective charge cycles. FIG. 10C shows the sixthcharge/discharge cycle, in the middle of which a 16 hour hold at zerocurrent was conducted, showing that the open circuit voltage (OCV)stabilized at about 4.1V. FIG. 10C also shows that there was asignificant polarization of ˜0.2V upon charge and discharge about theequilibrium voltage. This limits the state of charge during continuouscycling; as seen in FIGS. 10A and 10C, the charge curve did notterminate with a sharp rise in voltage. (The system was not charged tohigher voltages than 4.3V in order to prevent electrolytedecomposition.) The discharge capacity curves after the first cycle,seen in FIGS. 10B-C, showed a sharp drop-off in voltage that wasconsistent with incomplete charging, whereas the first discharge showeda gradual roll-off consistent with lithiation of the carbon anode tonear its capacity limit (FIG. 9). Other cells prepared similarly to theone reported in FIG. 10 behaved similarly.

Thus, these cells showed complete electrochemical functionality: theyheld an open circuit voltage, and charged and discharged reversibly withsubstantial utilization of the active materials contained within.Defining the basic “cell” to be all components contained within thevolume defined by the reticulated carbon sample (i.e., excluding thecurrent collectors, excess slurry, and container), the first-dischargecapacity data in FIG. 10B corresponds to a cell gravimetric energydensity of 120 Wh/kg. This may be compared with the theoretical upperlimit of 386 Wh/kg for a perfectly capacity-balanced LiCoO₂-graphitesystem with no inactive materials, and ˜140 Wh/kg for currentlyavailable lithium ion cells.

Example 5

This example describes a three-dimensional interpenetrating electrodenickel-metal hydride battery. Nickel metal foams are available, andsuitable for use as the stationary electrode, as described in Example 4,for electrophoretic fabrication of an aqueous electrolyte, nickelmetal-hydride battery. A nickel metal foam is infiltrated with asuspension of particles of its counterelectrode and optionallyconductive additives, which are suspended in an organic solvent oraqueous solution, including soluble binders. The zeta potentials of theparticle phases are measured or controlled through the methodologydescribed in Example 4. After electrophoretic separation and drying, thecell is infiltrated with an aqueous electrolyte, e.g., containing KOH,completing the battery.

Example 6

This example describes the use of a can in which a three-dimensionalinterpenetrating electrode battery is packaged as the working electrodefor electrophoretic separation. FIGS. 11A-B show two such cell designs.In FIG. 11A, a reticulated foam 110 is electrically connected to acurrent collector (tab) 112 exiting the conductive metal can 114, andisolated from the metal can 114 by insulating materials 116 such aso-rings, gaskets or sheets of insulating film or fabric. Uponinfiltrating the can 114 with a counterelectrode suspension, a potentialis applied between the can 114 and the current collector 112 so as toattract the suspension particles to the can 114 and repel them from thefoam 110. The polarity shown corresponds to the materials described inExample 4, where the foam 110 is carbon and the infiltrating suspensioncontains LiCoO₂ and Super P™. Thus, the suspension particles areattracted to the metal can 114 and repelled from the carbon foam 110.Suitable materials for the can 114 in this instance include aluminum andother metals stable at the positive electrode potentials in a Li-ioncell. The top current collector 112 connected to the carbon foam 110 iscopper or another metal stable at the negative electrode potential.

An alternative construction is shown in FIG. 11B, in which the foam 110is electrically connected to the can 114, while the current collector112 is electrically isolated by the insulator 116 from the foam 110. Inthis case, the polarity is reversed from the case illustrated in FIG.11A.

Example 7

Electrophoretic assembly of a 3D battery was carried out in theconfiguration shown in FIG. 17. The cathode formulation consisted ofacetone (6 g), PVdF (0.1 g), LiCoO₂ (0.2 g), and Super P (0.01 g). Alower current collector consisting of Pt mesh was placed onto the bottomof a 10 mL beaker. A cylindrical piece of reticulated carbon foam (60ppi) of ˜16 mm diameter by ˜3 mm height was attached to a second Pt meshcurrent collector, and placed above the first Pt mesh current collector,as shown in FIG. 17, such that they were separated by ˜1 mm. The cathodesuspension, which has a low viscosity, was added so that it filled thevessel well above the upper Pt mesh current collector attached to thecarbon foam. A dc voltage was then applied between the upper and lowerPt mesh current collector, with the lower current collector at positivepotential and the upper at negative potential. FIG. 18 shows the currentmeasured between the two current collectors as a function of time, fortwo values of applied voltage. At 4.2V, the current remains significant(>0.5 mA) even after 3 hours. However, at 10V, the current drops rapidlyand is below 0.1 mA after 4 h, effectively showing electrical isolation.This assembly, after drying and infiltration with liquid electrolyte asin Examples 2 and 4, shows lithium ion battery functionality.

Example 8

This example describes the use of bridging between two electrophoresiselectrodes to form a single battery electrode. FIGS. 12A-B shows the twostep deposition process for the electrophoretic assembly of a battery.In the first step, a set of 4 electrodes (Abtech Scientific, microbandelectrodes: 10 microns wide, 20 microns pitch, 3 mm in length) weresubmerged into a mixture containing acetone as a solvent, 2.8 wt % MCMBcarbon (5-8 micron, 6-28, Osaka Gas Co.) and 0.55 wt % polymer (Kynar2801). A potential of 5V was applied between the pair of electrodes onthe left in FIG. 12A for 20 seconds and then the microband was removedfrom the solution with the voltage still being applied. As observed inFIG. 12A, the carbon deposited as to bridge between the two electrodes.In the second step, the same set of electrodes were submerged into amixture containing acetone as a solvent, 6 wt % LiCoO₂ (Seimi,spelling?) and 0.46 wt % polymer (Kynar 2801). The mixture was allowedto settle for 3 hours, effectively decreasing the particle concentrationin the mixture. A potential of 5 V was applied between the pair ofelectrodes on the right in FIG. 12B for 3 minutes and then the microbandwas removed from the solution with the voltage still being applied. Thesample was then immersed in a liquid electrolyte consisting of a mixtureof ethylene carbonate and dimethyl carbonate with 1M LiPF₆. FIG. 13shows the charge and discharge for cycle number 40 for the batterypictured in FIGS. 12A-B. The battery was charged at 5 nanoAmperes to4.2V and discharged at the same current to 3V. The typical charge timewas 550 seconds and typical discharge time was 400 seconds and at cycle40 the battery had a capacity of 1.7 nAh.

An alternative mixture was made to demonstrate that LiCoO2 can also beelectrophoretically deposited by bridging. FIGS. 14A-B show the two-stepprocess to make a battery by electrophoretic deposition on a set of fourelectrodes (Abtech Scientific, microband electrodes: 20 microns wide, 40microns pitch, 3 mm in length) where both of the battery electrodes aredeposited by bridging. In the first step, the electrodes in FIG. 14Awere submerged in a mixture of 1-2 micron carbon (5 wt %) and acetone(no polymer) with a potential of 4V applied the right set. In the secondstep, the electrodes in FIG. 14B were submerged in a mixture containingacetone as a solvent, 9 wt % of LiCoO₂ and 5 wt % polymer (PVdF, 60,000MW). The mixture was not allowed to settle before electrophoreticdeposition. Electrophoretic deposition was performed at 4V for 5 secondsand bridging of the LiCoO₂ is observed in FIG. 14B.

Example 9

This example describes the dependence exhibited of the electrode onwhich particles with the absolute voltage and electric field between theelectrodes. FIGS. 15 A, B and C show the deposition from a mixture of 1wt % LiCoO₂ in acetone at 2, 2.5 and 3V, respectively, on 20 micron widePt electrodes with 20 micron gaps. This corresponds to electric fieldsbetween the electrodes of 1000, 1250 and 1500 V/cm, respectively. Atthese potentials and fields, the direction of deposition follows themeasured zeta potential, in that the particles deposit on the positiveelectrode. Additionally, these figures show that particles deposit onthe electrodes at low voltage and field (FIG. 15A) and bridge acrosselectrodes at higher voltage and field (FIGS. 15B,C and 16A,B and C).FIGS. 16 A, B and C shows the deposition observed at a higher voltage of5V (field of 2500 V/cm) from a similar mixture and on similarelectrodes. At this higher potential and field, the LiCoO₂ particlesdeposit at the negative electrode. The change in the direction ofparticle deposition is due to combined effects of electrochemicalreactions occurring at higher voltages and magnitude of the field.Similar behavior showing a switch in the electrode of deposition withincreasing voltage and electric field was also observed MCMB carbonparticles.

Example 10

A pattern of terminals is formed on a flat or curved surface, saidpattern having an interdigitated, serpentine, or spiral configuration,and thereby allowing formation of a battery using the methods ofExamples 3, 8 and 9. FIGS. 19 and 20 show a serpentine and a spiralpattern, respectively. Depending on the width and separation of theterminals, and the particle size of the deposited material, batteries inwhich the electrode width and spacing are as small as a few nanometerscan be fabricated. Larger dimensions from as submicrometer up to tens orhundreds of micrometers can also be fabricated. Such batteries allow thecreation of a 2-dimensional (in the case of a flat substrate) batterywith a single set of terminals connecting to an external device, makingmore efficient use of the available area than a multiplicity of linearbatteries as in Example 3, each separately connected to the externaldevice. The height of such an array can vary considerably and can be astall or even taller than the narrowest dimension of the pattern. Thatis, the height to width ratio of the deposited material can range from avery small value to over unity. This allows the total thickness (height)of such batteries to be controlled, and in some cases the thickness canbe many micrometers. As such, the energy (mAh) per unit area of thesubstrate in such batteries can be much greater that those ofsolid-state thin film batteries, in which the deposited film thicknessesare typically a few micrometers or less.

Example 11

This example is directed towards the fabrication of microscopic ornanoscopic “pinpoint” batteries, providing an unobtrusive power sourceof very small volume, typically less than 1 cubic millimeter; and, insome cases, less than 0.1 cubic millimeters. The methods of Examples 3,8 or 9 are applied to a pattern of terminals in which only a verylimited area of the terminal is exposed to the medium from which theelectroactive material is deposited. Thus deposition occurs in alocalized area on any suitable substrate, the specific dimensions ofwhich are determined by the dimensions of the terminals and thedeposited particles, suspension composition, and deposition conditionssuch as time, voltage, electric field, etc. The localized area may be,for example, less than 1 micron squared, less than 100 nanometerssquared and, in some cases, less than 10 nanometers squared. FIGS. 21and 22 illustrate configurations of terminals allowing such deposition,corresponding to the methods of Example 3 and 8 respectively. In FIG.21, two terminals are provided, at each of which an electroactivematerial is deposited, resulting in a pair of electrodes comprising adevice. In FIG. 22, four terminals are provided, and between each pairof terminals, deposition of particles limited by particle bridging iscarried out, to create a pair of electrodes comprising a device.

As will be apparent to one of skill in the art from a reading of thisdisclosure, the present invention can be embodied in forms other thanthose specifically disclosed above. The particular embodiments describedabove are, therefore, to be considered as illustrative and notrestrictive. The scope of the invention is as set forth in the appendedclaims, rather than being limited to the examples contained in theforegoing description.

1-21. (canceled)
 22. A bipolar device including a first terminal and asecond terminal made by a method comprising providing the firstterminal; providing particles of a first electroactive material in amedium; providing the second terminal electronically connected to asecond electroactive material; generating a field causing particles ofthe first electroactive material to form an electronically continuouselectrode, and creating an electronically insulating separation betweenthe first and second electroactive materials; and preserving theelectronically insulating separation between the first and secondelectroactive materials.
 23. The bipolar device of claim 22, wherein themethod further comprises depositing particles of the first electroactivematerial on the first terminal thereby forming an electronicallycontinuous first electrode; and generating a second field causingparticles of the second electroactive material to deposit on the secondterminal, thereby forming an electronically continuous second electrode.24. A method of making an electrode comprising: providing a firstterminal; providing conductive particles of an electroactive material ina medium; providing a second terminal; applying an electrical potentialbetween the first and the second terminal to deposit conductiveparticles of the electroactive material at the first terminal therebyforming an electronically continuous electrode; forming a continuousbridge of conductive particles of the electroactive material between thefirst and second terminals; and removing the applied electricalpotential.
 25. The method of claim 24, further comprising: providing athird terminal; providing conductive particles of a second electroactivematerial in a medium; providing a fourth terminal; applying anelectrical potential between the third and the fourth terminals todeposit conductive particles of the second electroactive material at thethird terminal thereby forming a second electronically continuouselectrode; forming a second continuous bridge of conductive particles ofthe second electroactive material between the third and fourthterminals; and removing the applied electrical potential.
 26. Anelectrode made by the method of claim
 24. 27. A battery comprising: asubstrate; a first terminal; a second terminal; and a localizedconductive region comprising electroactive material formed on thesubstrate and surrounded by an insulating region, wherein at least oneof the first or second terminals is electronically connected to theconductive region.
 28. The battery of claim 27, wherein the localizedconductive region has an area of less than 100 nanometers squared. 29.The battery of claim 27, having a volume of less than 1 cubicmillimeter.